Benzanthrone selenoethers



Patented Apr.

'sfymnietrieal configuration; FT 7 i. U. s. Patentll,965,85 5 issued uiy 10,'1e34,

agents, etc. By this ethers are produce m i selenols, hydroselenides orrselenophenols.

metal salts of the selenols V mmgtOn DeL No Drawing. ADp

3 9 9 r BENZANTHRONE SELE Melvin A. Perkin E.- I. du' Pont de Nemours &' a corporation of cati bum

s; Milwaukee, Wis., assignor to Company, Wil- Delaware onDen'ibr 20, I933,

Y mins."(0116 4601 8*: V

from solvent, proc'esss symm d when the b enzanthronyl- Bzl-benzanthrone ethers are produced when the two reacting coiiipounds arenotesimilarly substituted.

Incarrying out th s reaction, theuse of ap-e compounds; I I Without any intention of being limited thereby, thefollow'ing specific examples are given to more fully illustrate the principles of my inven v tion. "The parts used. are by weight. t

- .1 i Example! v 3 3 .l' p eirtes of Bzl-benzanthroner-sodinm selenolate (obtainable from Bzl -ha,logen-benzan thronei by treatment with alkali-selenide and saltlng out Of the reactionfprodlict after'filteringelf thebenzainthrohylelenide formed asa b Example? I H 6 parts of f Bzl, Bzl-benzanthronyl-diselenide KM. J3. about 240,C.,Vmade by air Oxidation of a.

for about hours. At the end of this time the when dissolved in sulfuric acid. mixture is then cooled to about 60 and washed with The reaction 0., filtered, o-dichlorobenzene, alcohol, and

water in the order named. Thus there is obtained a yellow-brown solid which gives an intense green-blue coloration in sulfuric acid. The yield isfrom 8 to 9 parts, showing that there must be actual condensation between the brom throne and the diselenide.

Example 3 If, in Example 2, 5.2 parts of Bzl-chloro-berizanthrone (M. P. 180 C.) is usedplacebf 6 parts of Bzl-bromo-benzanthrone, a

yields. that of Examples 1 and 2.

Example 4.--Preparation of cm unsymmetrically substituted B21, Bel'-benzanthronyZ-sele1tide 6 parts of 6, B21-dibromofbenzanthrone(ll/Ll. 257?. C.) and 45 parts of B21, B'z1' -benzanthrony1- diselenide are slurried in 100 parts of jo-dichlorobenzene. 1.5' partsof anhydrous sodium acetate are added and the whole heated to reflux'for about 10 hours, whereupon a rich yellow-brown melt is obtained. Upon, cooling slightly and filtering, there is obtained in'h gh yield a yellow-brown solid which gives a greenish bluefcoloration in sulfuric acid; I n n Examples 7.4 parts of BZI-bromO-BZZ acetamino b'enz- .anthrone' (prepared for example by brominating B22-acetamino-benzanthrone-M. P. '265' C.-in

glacial acetic acid), 6.2 parts of Bzl, Bz1'-benzanthronyl-diselenide and 2 partsof anhydrous sodiumacetate are stirred into 80 parts of molten naphthalene, and the mixture heated at the boil mass is cooled slightly, drownedin solvent naphtha, filtered and the residuev washed'with alcohol and water to remove salts. -ere,i'sthusobtained a yellow-brown solid which fdissolves in sulfuric acid, giving a viole t-br'own coloration, does not vat, but when heated with alcohol. and potassium hydroxide gives a greenish-blue melt. Upon dilua dark blue vat is obtained "from which cotton is dyed blue shades whichbecome bluish-gray upon rinsing and drying the liner.

' This m'ono-acetylamino substituted compound differs materially from the unsubstituted Bzl, Bzl benzanthronyl selcnide, which gives a violet dyeuponfusion. Q i

. 7 Example 6- 10 parts of amino-B21gchloro benzanthrone (made by reduction of the'nitro-Bzl-chloro benzr anthrone obtained by nitration of ,Bz'l-chlorobenzanthrone in of concentrated nitric'acid) 11 partsof Bz1,'Bzlbenzanthronylediselenide, 0.1 part of copper powder ando parts 'oficalcium, hydroxide are stirred at ordinary temperature into 120 parts'of tetrahydronaphthalene,JIhe mixture is then heated to reflux GOO-205C.) .until a test Portion dissolves in sulfuric acid with a green coloration. (The initial materlals' together give a red-violet coloration-in sulfuric acid.) This requires from 5 to 8 hours. After cooling, the thick'brownish mass is" filtered, andtheresidual solid washed, first with solvent naphtha, then.with alcohol and finallywith hot dilute" hydrochloric acid'. The

monoamino-Bzl, B21. benzanthronyl selenide is benzan- V throne (M. P. 250-254 similar ;re sult is obtained, although somewhat longer time of reaction is advisable in order :to realize'best The product obtained is identical with tion) rarer introduced benzene and the mass heated to refiuxuntil a test portion gives a blue-violet coloration in sulfuric tered off and washed sulfuric acid with one equivalent obtained in excellent yield as a brownish solid which dissolves in sulfuric acid with an intense moss-green color, and which yields upon fusion in alcoholic caustic potash a blue-violet dyestuff which dyes cotton from a reddish-blue vat blueviolet shades, which by the action of chlorine are converted to reddish-navy blue shades.

I 'Emample7 6.5 parts of BZl-benzanthrone-sodium selenolate plus salt (containing 4.5 parts of 100 seleno- Bzl, Bz2-dichloro-benzan- C. and obtained by diazotization of Bzl-amino-Bz2-chlorobenzanthrone, followed by treatment with cuprous chloride soluinto 100 parts of trichlorolate) and all) parts of acid." After cooling, the brownish solid is filwith alcohol and water. The. .monochloro-Bzl, Bzl' -benzanthronyl selenide thus obtained gives a blueviolet coloration in sulfuric acid solution and fuses in alcoholic caustic potash to give an intense blue melt. After dilution and vatting, a violet-blue vat is obtained from which cotton is Example 8 30' parts of o-amino-Bzl chloro-benzanthrone (made, forexample, by reduction of the nitro Bzl-chloro benzanthrone- M. P. 282? C.-pro'- duced by nitration of Bzl-chloro-benza'nthrone in nitrobenzenebymeans offuming nitric acid) 33 parts of B21, Bzl-benzanthronyl-dise1enide 'and15' parts of sodium bisulfite are introduced into 600 parts of high boiling kerosene'and the mixture heated to"185190 C. for several hours, until a test portion gives a bluish-green coloration when dissolved in ulfuric acid. The reaction 'mass isthen cooled slightly and filtered. The solid may be freed from kerosene by a suitable method; for instance, by steaming, of'the cake and subsequent filtration. The brownish solid thus obtained is very similar to the monoamino- Bzl, -Bz1f benzanthronyl-selenide obtained "as. in Example 6; Its solution in sulfuric'acid possesses an intense moss-green color and fusionrwith alcoholic caustic potash yields a blue melt. The 'dyestuff resulting hasa reddish-blue vat and dyes cotton very blue shades of violet somewhat similar to those producedby dibenzanthrone.

According to the present invention, diselenides are convertible into valuable sel'enoetherswhich yield isoviolanthrone or derivatives thereof upon fusion. It furthermore provides a. method for preparing unsymmetrical substitution products of B21, Bzl'-benzanthronyl-selenide whichit' is difficult or impossible to obtain byothermethods. Whenthe benzanthronyl-selenolate is used in the reaction, the addition of acid binding agents is of course notnecessary, since the alkali-metal present in the selenolate'is' sufficient to take up under the conditions; used. The potassiumselenolates may be substituted for the sodium salts usedin theabove examples.

Inthe following claims, the terms. gen-benzanthrone, "fa IBzl-benzantlir'onyl-seledyed instrong violet shades n 7 similar to those produced by isodibenzanthrone.

consisting of a Bzl-benzanthronyl-selenolate, a B21-benzanthronyl-selenol, and a 321, Bzl'-benzanthr0nyl-diselenide.

2. In the preparation of benzanthronyl selenoethers, the step which comprises heating a Bzlpound of the group consisting of a Bzl-benzanthronyl-selenolate, a Bzl-benzanthronyl-selenol,

and a 321, Bz1-benzanthrony -dise1enide in the presence of a. solvent.

3. In the preparation of benzanthronyl selenoethers, the step which comprises heating a 321- halogen-benzanthrone compound'with an alkalimetal-B21-benzanthronyl-selenolate in the pres- I ence ofa solvent.

4. In the preparation of benzanthronyl seleno-i ethers, the step which comprises heating a 321- Bzl' benzanthronyl-diselenide in the presence of an acid binding agent and a solvent for at least one of the reactants.

5. In the preparation of benzanthronyl selenobenzanthronyl-selenol in the presence of an'acid binding agent and a solvent for at least one of the reactants. v

6. An unsymmetrical Bzl, Bz1'-benz'anthronylselenoether. i

- MELVIN A. PERKINS, 

